Nonsiccative complex



as Paras OFFlCE- oNsrcoA'rrvE commrx Carleton Ellis, Montclair, N.'.l., assignor to Ellis- Foster Company, a corporation of New Jersey No Drawing. Application September 14, 1927,

e Serial No. 219,552

6 claims. (or. zoo-4 Tins invention relates to synthetic resins and It will be noted that these reactive oxygenated baisams or analogous solid to liquid products debodies are chemically diflerent as a class from rived irom non-drying animal or vegetable oils the non-drying giyceride oils and their fatty or their fatty acids and a reactive oxygenated acids. Physically also they usually are different,

5 body such as a polyhydric alcohol, preferably with e. g., many are water soluble or hygroscopic sub- 5 the inclusion of a crystalline acid or anhydride stances. of the aliphatic or aromatic series, as will be more Crystalline organic acids or acid anhydrides, fullyhereinafter described. lactones, and so forth, likewise include a wide The non-drying glyceride oils include lard oil, range of acid bodies, which, as set forth in afore- 9 tallow oil, neats-foot oil, palm kernel oil, cocoanut said Serial No. 61,839 may comprehend aliphatic 10 oil, and the like. The invention will be illusacids or anhydrides such as succinic, tartaric, trated by examples of products prepared with the citric, malic, maleic, fumaric, pyruvic, azelaic, aid of cocoanut oil or its fatty acids. It should sebacic, and the like, or aromatic acids or anbe understood, however, that other non-drying hydrides such as phthalic, diphenic or other polyoils or their fatty acids such as palm kernel oil basic or polycarboxylic acids, or benzoic, salicylic 5 or its fatty acids, may replace the cocoanut oil or or similar monobasic acids. 'I'heemployment oi its fatty acidaas set forth illustratively in the substances yielding such acids is not precluded. subloined examples.- The employment of cyclic Mixtures of the crystalline acids likewise may be acids such as naphthenic acids likewise is not preemployed. While I'prefer to use crystalline acids eluded. I as aforesaid! do not wish to exclude non-crystal- 20 The aioresaid reactive oxygenated bodies comline acids, such as lactic, in some cases. It will prise a wide range of substances of differing be noted that the crystalline acids illustratively chemical and physical properties. The followmentioned have as a rule less than 12 carbon I ing will serve in an illustrative way: atoms in the molecule and in this respect differ e l. Glycerol, in its various forms' -dilute, confrom the oil-acids which have 12' carbon atoms, 25 centrated, crude or refined. w 7, 'e. g., lauric acid of cocoanut oil, or higher, e. g.,

2. Polyglycerols, or a mixture or polyglycerols those of various non-drying oils containing 16 819691131- or 18 carbon, atoms in the-fatty acid component. Vaflws w flushes-ethylene P As set forth in Serial No. 61,839 page 14, in

' b d n ed 1 t 1 general I-prefer to employ: "on theone hand, 3 by slfitabrlxalye 1m:- vmit xr z s 1:; 33:3 52: acids containing-ten carbon atoms or less, these times obtained from this source-may b used o 1 mostly) fairly water'solume and crystal aqvantaga The employment of 81 01s in this zable (lactic acid an exception) reactive with the oxygenated organic bodies stated, these like- 35 35 way is referred to in m co ndin a lication Serial No. 61,839 filed 00 t. m fieza or 31 1 am the wisemquenfly water-Whig even scopic (glycerol, for example) and conferring present a 'lication is a continuation in part.

4. Poiyhydric alcohols containing a substituent wamr'reslstanw by reaction'with a Water-111501- in the hydroxyl, e, g n o thm f pmpyl ble fatty oil (or fatty acid) having at least 12 ether oi glycerol, The m n ethyl th of carbon atoms 'in the fatty acid molecule; ,such 40 ethylene glycol has one hydroxyl free for reactive acquirement f W r r nc b n wi h ut Was. The glycerol and th glycol d i loss of solubility in various common volatile ortives behave quite differently in the reaction, owganic solvents or mixtures of these. This feature ing to different polymerizing tendencies and other of solubility is an important one when the product proper ties. is to be used as a coating medium in paints, var-- 5. lycol ethers (inte'r-ethers) nishes, nitrocellulose, lacquers, and the like. The condensation of two or more molecules of .While the invention does not exclude the produca givenglycol yields inter-ethers; e. g., two mole- 'tion of insoluble complexes, I am, in the main, cules of ethylene glycol condense to .dihydroxy seekingto prepare water-resistant products solu- 5 diethyl ether, three molecules give the dihydroxybi e in various volatile organic solvents and prefertriethyl diether, and so on. e 1 ably compatible with nitrocellulose or other cellu- ,61: :Chlorhydrins or other halohydrin. lose esters or ethers and the like, thereby to ob- Homologues of ethylene oxide, for exampl tain a product of v lue in the coating and plastic butylene oxide. field.

out agitation to 300 Example 1 Parts by weight Glycerol (98 per cent 0. P.) '94 Cocoanut oil 100 Para toluyl ortho benzoic acid 720- were heated together with- C. yielding an amber-colored resin of acid number approximately 30. soluble in butyl acetate, toluol and various other ordinary nitrocellulose lacquer solvents or vehicles. Although soluble in hot denatured alcohol, the solubility in the cold alcohol was not These ingredients great.

" receptacle was equipped case may be) can be viscosity,

'Phthalic anhydride Example 2 Parts by weight Mixed ethylene and propylene glycols (about equal parts) ..'...a Fatty acids of cocoanut oil likewise were heated to 300 0'. without agitation until the acid number was 28.6. A-soft sticky resin of dark amber color resulted. was soluble in benzol, toluol and xylol, also in butyl acetate and other esters and in various The ingredients solvent mixtures. The resin was compatible with nitrocellulose.

I Example 3 i Parts by weight Glycol-ether (dihydroxy diethyl mono ether) 10.6 cocoanut oil 40 Phthalic 'anhydride 148 On heating these substances together to induce reaction, agitation was employed and the reaction with an air-cooled reflux C. until the acid a viscous balsam It was solublein On heating to about 300 number was approximately 22 of toluol alone. patibility with solved in this solvent mixture.

The proportions of nitrocellulose in coating used in relatively-high proportion, say from 2 to 10 parts by weight to one partof nitrocellulose.

-' The nitrocellulose used may be of low or high It was ,low acid number.

balsam in making molded products, plastic masses for sheeting to form the tread of felt base floor covering, and for various other purposes.

By employing a non-drying oil or its fatty acid and especially by reacting a substantially or relatively saturated glyceride oil such as cocoanut oil (or its free acids) I reduce the tendency to oxidation changes in a coating on long ex posure, and the stabilization thus effected I consider to be of material benefit.

Coccanut oil or other animal and vegetable oils embraced herein may be chilled and pressed to secure low cold test grades and either the press cake or the more liquid 'glycerides employed in the reaction. The free fatty acids themselves likewise may be chilled and pressed to secure different grades of varying fluidity.

Generally speaking, I prefer to employ natural glycerides or their fatty acids which are low in stearic or similar solid fats. In the case ofcocoanut oil, for example, chilling and pressing allows separation into a portion of higher melting point desired in confectionary manufacture, while the more liquid portions may be utilized in making products of the present invention. 1

stood that cold-test cocoanut oil or the fatty acids of corresponding titre may be used. The employment of a. non-drying substantially oxygen-stable cold-test glyceride oil or its fatty acids constitutes one of the specific forms of the invention. I

The free fatty acids of the non-drying oils are considerably more reactive than the glycerides from which they are derived. They. are used 1 advantageously with glycerol or other po'lyhydric alcohol tending to readily form polymerization products which are insoluble or even infusible. Being more'reactive, the desired reduction in acid number may be brought. about beforethe final polymerization stages" set in. Thus soluble resins acid number areand balsams of relatively low obtained without difilculty.

For many purposes, especially in making coating compositions; a low acid number is desirable. There is less tendency to'livering with basic pigments and in the case of nitrocellulose lacquers a low acid number v the composition is to be .used for insulating puris desirable. A complex which oi thepresent invention. This result as illustrated by the foregoing examples and by the data set forth in Serial No. 61,839 noted above, is carried out by the employment acids of the natural glycerlde' oils. These oil are more briefly termed have a action on the incipient resin crystalline organic acid and glycerol, pentaerythritol or other polyhydric alcohol. Without the fluxing effect of the oil-acid The animal and selves used with glycerol the proportion of slyceride' is considered safer. Also, if

vegetable glycerides themdo not have this nuxing action and when of the free fatty preferably should be small, or a non-acid flux, capable of entering into the reaction be employed. Such reactive non-acid fluxes are found for example in the glycolethers, dihydroxy diethyl mono ether (CHzOHCl-IaQCHzJCHzOH) being an illustration of a substance very effective for the purpose.

- By proceeding in accordance with the disclosures of the present invention I am thus able to control acid number with respect to solubility and thereby easily and cheaply to obtain resins,

balsams and other complexes of value in the coating, plastic and insulating industries.

' The distilled fatty acids of animal and vege-" table oils also may be used in making the nonsiccative complex. Drying or semi-dryingoils may be blown to such an extent that they lose siccative properties almost completely. Reactive.

blown oils or their fatty acids, having substantially non-siccative qualities are included with the raw materials employed in the present invention) These include the blown derivatives of com, cotton, soya, castor, rape and other vegetable (or animal) oils. Blowing to a condition of substanti'al non-siccativity introduces'oxygen at double bonds and thus creates loci of condensation.'

In the illustrative examples all the constituents are reacted together simultaneously. This, however, need not be the casein all circumstances as the'reaction may be started with, say, two of the ingredients and the third (and fourth, etc., if

used) added later,'usua1ly avoiding attainment Y of conditions of instability leading to formation of infusible polymers.- For example, if phthalic. anhydride and glycerol '(a mix which readily forms. insoluble condensation bodies) are being heated together, the reactive fluxing oil-acid or the neutral reactive flux, e. g'., glycol-ether, pref erably should be added in advance of material lieadway'in the formation of insoluble products of condensation.

Thus the order of mixing may be varied and the process of the present invention is not restricted to the order in which the ingredients are introduced into the reaction'receptacle. Broadly considered, the process comprises the heating to a combiningtemperature of a mixture containing. a reactive'oxygenated body as aforesaid, an acid body containingless than 12 carbon atoms and another acid body containing at least, 12 carbon atoms, such body preferably being an oil-glycer- V ide or oil-acid having substantially non-siccative properties, and continuing-the heating until a non-siccativecomplex of low acidity and'useful solubility resulta, Instead of normal triglycerides the mono or -diglycerides may be reacted with the sub-l2- carbon acid and a. polyhydric alcohol or-oth'er 'non-aci'd reactive oxygenated organic body aforesaid.

The sub-12-carbon acid may contain substituents such as chlorine, bromine, sulphonic or nitro' groups. The 12 carbon or super-12-carbon acid likewise may carry substituents.

The term crystalline organic acid embraces those .acids which are definitely solid and crystalline at room temperature (20-25". C.) and does not include as an essential component the lower fatty acids of three carbon atoms or less (liquid at such temperatures) used in conjunca higher fatty acid although incidental use is permissible in some cases. On the other hand such liquid lower fatty acids may be used in conjunctidn with an aromatic monobasic'acid such as benzoic, toluyl-benzoic, salicylic and the cylic; 6.; Dhthalic, 8; trimellitic, 9.

sebaclc acid.

like or polybasic acidssuch' as phth'alic, tereph thalic, diphenic and so forth; all inter-reacted with a fatty acid of the lauric type of 12 carbon atoms or higher but specifically those oil-acids which form triglycerides soft or liquid at room temperature. For the purpose of the present invention I prefer the natural glyceride oil or oilacids as free as possible from stearic acid. When complexes containing a high or influential proportion of stearic acid are admixed with nitrocellulose in solution there is a tendency to form greasy films which is avoided by using saturated or-ncn-d'rying oil-acids of lower melting point.

Considering the lower fatty acids to be those up to and including three carbon acids as aforesaid, the intermediate-carbon fatty acids are those ranging from four to ten or eleven carbon,

atoms. The oil-acids start substantially with lauric acid (12 carbon atoms) and rangeupw'ard in molecular weight and consequently in the number'of carbon atoms.. These high-carbon acids are restricted in the present invention to saturated fatty acids or to non-drying acids and mixtures of such acids.

In the aromatic series most of the acids or anhydrldes contemplated fall in the group of intermediate-carbon acids, e. g., benzoic, 6; sali- Other aromatic or carbocylic acids not falling into the intermediate-carbon class-but contemplated for the production of certain species of resins hereunder are diphenic acid, toluyl .benzoic acid, mellitic acid, and so forth. I

The'high-carbon acids of the aromatic or car bocylic series tend to produce harder products than results by the use of many of the intermediate-carbo'n acids or those of intermediate molecular weight. 1 f

Oneiapplication of. lower fatty acids is that of using acetic anhydride on the otherwise completed resin or balsam to acetylate any free hydroxyl remaining. v,This' procedure allows of increasing water-resistance when free'hydroxyl is ,in various organic solvents and which may be caused to yield, on saponiflcation,-' the original acids (as their salts) and the oxygenated body,

. such as a polyhydric alcohol, in free state. Ex-

ceptionszto this are bodies which break down or crack in the heatingoperation of preparation to give'so'mewhat' dissimilar bodies on saponiilca tion. I A specific form ofthe present invention is that 1 of using a crystalline acid of a higher number of carbon atoms than 11 or 12-such as the substituted benzoic acids containing a second benzene ring, e.-g., benzoyl benzoic acid, toluyl ben-- zoic acid and ,even acids of still higher 111018011? lar weight such as naphthalene benzoic acid.

WhatIclaim is: I 1. A composition of matter comprising the reaction product of polyglycerol and sebacic acid.

2; A composition of matter comprising the reaction product of blown castor oil, glycerol, and

3. Composition of matter. comprising therein;-

.45 water due to this hydroxyl may, be acetylated by tion product or blown castor oil, glycerol, and

azelaic acid. 4. Composition of matter comprising the reaction product of blown castor oil, a, polyhydric 5 alcohol having-over two hydroxyl groups, and

sebacic acid. 5. A composition of matter comprising the reaction product of blown castor oil, a. p lyhydric alcoho'rl r'cving over two bydroxyl-groups, and an aliphaticzdlbasic acid.

' 6. A composition of matter comprising tho-re? action product of blown castor oil, a polyhydric alcoholhaving over'. two hydroxyl groups, and 5 azelaic acid. I

. CARLETON ELLIS. 

